Microbicidal N-alkoxycarbonyl-alkyl-N-substituted acetyl-anilines and -naphthylamines

ABSTRACT

Compounds of the formula   &lt;IMAGE&gt;   in which Ar is 2-alkyl-, -alkoxy- or -halo-methyl-phenyl or  alpha -naphthyl, each of which is further substituted, R1 is 2-furyl, 2-tetrahydrofuryl, alkenyl, cyclopropyl,  beta -alkoxyethyl, hydroxymethyl, triazolylmethyl, imidazolylmethyl, pyrazolylmethyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio, alkylsulfinyloxy, dialkylaminosulfinyloxy, phosphoric or thiophosphoric esters or amides, or alkylcarbonyloxy, R7 is hydrogen or optionally-substituted methyl or ethyl, and R8 is alkyl optionally substituted by alkoxy, are microbicidally, in particular fungicidally, active. Preferred compounds are those in which Ar is 2-methylphenyl, 2-methoxyphenyl, 2-chlorophenyl or  alpha -naphthyl, each of which is further substituted by azido, and each of R7 and R8 is methyl.

The present invention relates to microbicidally active acylalanine andacylnaphthylamine derivatives, to processes for producing them, tocompositions containing them as active ingredients, and to the usethereof for combating fungi and bacteria.

The novel compounds correspond to the general formula I ##STR2## whereinAr is a group of the formula ##STR3## R₁ is 2-furyl, 2-tetrahydrofuryl,C₂ -C₄ -alkenyl, cyclopropyl, β-(C₁ -C₄)-alkoxyethyl or --CH₂ Z, eachbeing unsubstituted or substituted by halogen, and Z in the group --CH₂Z being

(a) --OH,

(b) -1H-1,2,4-triazolyl, 1-imidazolyl or 1-pyrazolyl,

(c) --S(O)_(n) --R₁₃

where R₁₃ is C₁ -C₄ -alkyl, and n is 1 or 2,

(d) --X--R₁₄

where X is oxygen or sulfur, and R₁₄ is C₁ -C₆ -alkyl, C₃ -C₄ -alkenylor C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy,

(e) --OSO₂ --R₁₅

where R₁₅ is C₁ -C₄ -alkyl, or mono- or di-(C₁ -C₃)-alkylamine,

(f) ##STR4## where X is oxygen or sulfur, R₁₆ is C₁ -C₄ -alkyl, C₁ -C₄-alkoxy or C₁ -C₄ -alkylamino, and R₁₇ is C₁ -C₄ -alkoxy or C₁ -C₄-alkylamino, or

(g) ##STR5## where R₁₈ is C₁ -C₃ -alkyl which is unsubstituted orsubstituted by C₁ -C₂ -alkoxy,

R₂ is C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy or halogen,

R₃ is --CH₂ OH, --N₃, ##STR6## where R' is C₁ -C₆ -alkyl or C₂ -C₄-alkenyl, each unsubstituted or substituted by halogen or C₁ -C₃-alkoxy, or it is unsubstituted or substituted phenyl, and X is oxygenor sulfur,

R₄ is hydrogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, halogen, --NO₂ or --NH₂,

R₅ is hydrogen or C₁ -C₃ -alkyl,

R₆ is hydrogen or C₁ -C₃ -alkyl,

Y is ##STR7## wherein R₇ is hydrogen, C₁ -C₂ -alkyl which isunsubstituted or substituted by halogen, --OH, --OC₁ --C₃ -alkyl or##STR8## R₈ is C₁ -C₄ -alkyl which is unsubstituted or substituted by C₁-C₂ -alkoxy,

R₉ is hydrogen or methyl,

R₁₀ is hydrogen or C₁ -C₃ -alkyl,

R₁₁ is C₁ -C₄ -alkyl, whereby R₁₁ 's together can form a C₂ -C₃-alkylene bridge which is mono- or poly-substituted by C₁ -C₃ -alkyl,

R₁₂ is hydrogen, halogen, C₁ -C₂ -alkyl or phenyl, and

X is oxygen or sulfur.

The substituents R₃, R₄ and R₅ of the naphthylamine derivatives embracedby the formula I fluctuate, so that each of these substituents canoccupy the position 2, 3, 4, 5, 6, 7 or 8 in the naphthyl ring.

By alkyl or alkyl moiety of another substituent are meant, depending onthe given number of carbon atoms, for example the following groups:methyl, ethyl, propyl and butyl, as well as isomers thereof, such asisopropyl, isobutyl, sec-butyl or tert-butyl. Alkenyl is for example:vinyl, propenyl-(1), allyl, butenyl-(1), butenyl-(2) or butenyl-(3); andalkynyl is particularly propargyl. Halogen here and in the following isfluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

A preferred group of microbicides according to the invention comprisescompounds of the formula I having the following combination ofsubstituents:

R₁ is 2-furyl, 2-tetrahydrofuryl, C₂ -C₄ -alkenyl, cyclopropyl, β-(C₁-C₂)-alkoxyethyl or --CH₂ --Z, where Z is

(a) --OH,

(b) 1H-1,2,4-triazolyl or 1-imidazolyl,

(c) --S(O)_(n) --R₁₃

where R₁₃ is C₁ -C₂ -alkyl, and n is 2,

(d) --X'--R₁₄

where X' is oxygen or sulfur, and R₁₄ is C₁ -C₆ -alkyl, C₃ -C₄ -alkenylor C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy,

(e) --OSO₂ --R₁₅

where R₁₅ is C₁ -C₂ -alkyl, or mono- or di-(C₁ -C₂)-alkylamine,

(f) ##STR9## where X" is sulfur, R₁₆ is C₁ -C₂ -alkyl, C₁ -C₄ -alkoxy orC₁ -C₂ -alkylamino, and R₁₇ is C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, or

(g) ##STR10## where R₁₈ is C₁ -C₂ -alkyl which is unsubstituted orsubstituted by C₁ -C₂ -alkoxy,

R₂ is C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy or halogen,

R₃ is --CH₂ OH, --N₃, ##STR11## where R' is C₁ -C₃ -alkyl or C₂ -C₃-alkenyl, each unsubstituted or substituted by chlorine or methoxy, andX'" is oxygen or sulfur,

R₄ is hydrogen, C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy, --NO₂ or NH₂,

R₅ is hydrogen or C₁ -C₂ -alkyl,

R₆ is hydrogen or C₁ -C₂ -alkyl,

Y has the meanings defined under the formula I, whereby R₇ is hydrogenor C₁ -C₂ -alkyl which is unsubstituted or substituted by halogen, --OH,--O(C₁ -C₂)-alkyl or ##STR12## R₈ is C₁ -C₃ -alkyl which isunsubstituted or substituted by C₁ -C₂ -alkoxy,

R₉ is hydrogen,

R₁₀ is hydrogen or C₁ -C₂ -alkyl,

R₁₁ is C₁ -C₂ -alkyl, whereby R₁₁ 's together can also be C₂ -C₃-alkylene,

R₁₂ is hydrogen, halogen or C₁ -C₂ -alkyl, and

X is oxygen or sulfur.

A further preferred group of microbicides of the formula I ischaracterised by the following combination of substituents:

R₁ is 2-furyl, 2-tetrahydrofuryl, C₂ -C₄ -alkenyl, cyclopropyl,β-methoxyethyl or --CH₂ Z, where Z is

(a) 1H-1,2,4-triazolyl,

(b) --S(O)_(n) --R₁₃

where R₁₃ is CH₃, and n is 2,

(c) --X'^(v) --R₁₄

where X'^(v) is oxygen, and R₁₄ is C₁ -C₄ -alkyl, C₃ -C₄ -alkenyl or C₃-C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy,

(d) --OSO₂ --R₁₅

where R₁₅ is mono-(C₁ -C₃)-alkylamine,

(e) ##STR13## where X^(v) is sulfur, and R₁₆ and R₁₇ independently ofone another are each C₁ -C₃ -alkoxy, or

(f) ##STR14## where R₁₈ is C₁ -C₃ -alkyl, R₂ is methyl, methoxy orchlorine,

R₃ is --CH₂ OH, --N₃ or ##STR15## R₄ is hydrogen, methyl, methoxy, NO₂or NH₂, R₅ is hydrogen or methyl,

R₆ is hydrogen or methyl,

Y has the meanings defined under the formula I, whereby

R₇ is C₁ -C₂ -alkyl which is unsubstituted or substituted by chlorine,--OH, --OC₁ --C₂ -alkyl or ##STR16## R₈ is C₁ -C₃ -alkyl, R₉ ishydrogen,

R₁₀ is methyl,

R₁₁ is C₁ -C₂ -alkyl, whereby R₁₁ 's together can also be C₂ -C₃-alkylene,

R₁₂ is hydrogen, bromine, iodine or C₁ -C₂ -alkyl, and

X is oxygen.

Compounds of the last-mentioned group wherein R₃ is azido (--N₃) areparticularly preferred active substances, especially those wherein Y isthe group --CH(CH₃)COOCH₃ or ##STR17##

The following individual compounds are to be emphasised on account oftheir pronounced activity against phytopathogenic microorganisms:

N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2-methyl-6-azido-aniline,

N-(tetrahydro-2'-on-fur-3'-yl)-N-methoxyacetyl-2,6-dimethyl-3-azido-aniline

N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-azido-aniline,

N-(1'-methoxycarbonyl-ethyl)-N-(2-tetrahydrofuryl-carbonyl)-2-methyl-6-azido-aniline,

N-(1'-methoxycarbonyl-3'-hydroxy-n-propyl)-N-methoxyacetyl-2-methyl-6-azido-aniline,

N-(1'-methoxycarbonyl-ethyl)-N-methylaminosulfonylacetyl-2,6-dimethyl-3-azido-aniline,

N-(1'-methoxycarbonyl-3-hydroxy-n-propyl)-N-cyclopropylcarbonyl-2-methyl-6-azido-aniline,

N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2,3-dimethyl-6-azido-aniline,

N-(1'-cyanoethyl)-N-methoxyacetyl-2-methyl-6-azido-aniline,

N-(1'-methyl-2'-dimethoxy-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-azido-aniline,

N-(2'-methyl-3'-methoximino-n-propyl)-N-methoxy-acetyl-2-methyl-6-azido-aniline,

N-(tetrahydro-2'-on-fur-3'-yl)-N-methoxyacetyl-2,3-dimethyl-4-azido-α-naphthylamine,

N-(1'-cyano-ethyl)-N-methoxyacetyl-2,3-dimethyl-4-azido-α-naphthylamine,and

N-(1'-cyanoethyl)-N-(2-tetrahydrofuryl-carbonyl)-2,3-dimethyl-4-azido-.alpha.-naphthylamine.

Phenylacylalanines having microbicidal activity and their productionhave already been known for some time from the literature. In thisconnection, there are mentioned for example the following publications:German Offenlegungsschriften Nos. 2,847,287, 2,908,739, 2,920,435,2,922,759, 2,927,461 and 2,929,525, and also EP Nos. 5591, 12 703 and 17850.

The compounds of the present invention are distinguished by aparticularly uniform fungicidal activity, and by properties renderingthem especially tolerant to plants.

The compounds of the formula I can be produced in a known manner, forexample as described in the following. In the formulae II-VII, thesymbols Ar, Y and R₁ -R₆ have the meanings defined under the formula I.The symbol A denotes one of the usual removal groups, for example:alkoxy, benzenesulfonyloxy, p-bromobenzenesulfonyloxy, p-tosyloxy,trifluoroacetyloxy, lower-alkylsulfonyloxy, such as mesyloxy, orparticularly halogen, such as fluorine, chlorine, bromine or iodine,preferably chlorine or bromine.

PRODUCTION PROCESS

Active substances of the formula I can be produced:

(A) by acylation of compounds of the formula II ##STR18## withcarboxylic acids of the formula III or with reactive derivativesthereof; or

(B) by reaction of compounds of the formula IV ##STR19## with compoundsof the formula V, wherein A denotes a usual removal group; or, in thecase where R₃ is the N₃ group,

(C) by formation of the diazonium salts of the compounds of the formulaVI, and subsequent variable reaction as follows: ##STR20## or, in thecase where R₃ is the HOCH₂ group,

(D) by reaction of compounds of the formula VII with NaOH in acetone##STR21## wherein R" is C₁ -C₄ -alkyl; or, in the case where R₃ is oneof the groups ##STR22##

(E) by the following reactions of compounds of the formula Ib: ##STR23##wherein "Hal" is halogen, preferably chlorine or bromine. In the case ofreactions (a) and (b), they are preferably performed in the presence ofan acid-binding agent.

The following reaction conditions are advantageous for the statedproduction processes:

PROCESS A

In this process is preferably used a reactive derivative of a compoundof the formula III, for example the acid halide or acid anhydride or theester. The acid chloride or the acid bromide is particularly suitable.

The reaction temperatures are between 0° and 180° C., preferably between0° and 150° C., or at the boiling point of the solvent or solventmixture. The use of acid-binding agents or of condensation agents is insome cases advantageous. Suitable as such are organic and inorganicbases, for example tertiary amines, such as trialkylamines(trimethylamine, triethylamine, tripropylamine, and so forth), pyridineand pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine,and the like), oxides and hydroxides, carbonates and hydrogen carbonatesof alkali metals and alkaline-earth metals, as well as alkali acetates.

Formed hydrogen halide can in some cases be expelled also by means ofthe passing through of inert gas, for example nitrogen, from thereaction mixture.

The N-acylation can be performed in the presence of solvents or diluentsinert to the reactants. These are for example: aliphatic and aromatichydrocarbons, such as chlorobenzene, methylene chloride, ethylenechloride, chloroform, carbon tetrachloride and tetrachloroethylene;ethers and ethereal compounds, such as dialkyl ether (diethyl ether,diisopropyl ether, tert-butyl methyl ether, and so forth), anisole,dioxane or tetrahydrofuran; nitriles, such as acetonitrile orpropionitrile; N,N-dialkylated amides, such as dimethylformamide ordimethyl sulfoxide; ketones, such as acetone, diethyl ketone, methylethyl ketone, and mixtures of solvents of this kind with one another.The acylating agent itself can in some cases serve as solvent. Thepresence of a reaction catalyst, such as dimethylformamide, can be ofadvantage in performing acylation.

PROCESS B

The substituent A in the formula V is in this process one of thecustomary removal groups, for example alkoxy, benzenesulfonyloxy,p-bromobenzenesulfonyloxy, p-tosyloxy, trifluoroacetyloxy,lower-alkylsulfonyloxy, such as mesyloxy, or it is in particularhalogen, such as fluorine, chlorine, bromine or iodine, preferablychlorine or bromine. In this embodiment, the starting compound of theformula IV is advantageously firstly converted, with butyllithium orsodium hydride, into the corresponding alkali salt, or alternatively thereaction is carried out in the presence of an acid-binding agent, in amanner analogous to that of variant A, preferably with the addition ofcatalytic amounts of alkali iodide.

Further methods for synthesis of compounds of the formula I are givenfor example at the following places in the literature: Houben-Weyl Vol.11/2, p. 3 and Vol. 8, p. 653.

Some of the starting materials for the production of the compounds ofthe formula I according to the invention are novel, whilst some areknown. The novel starting materials can be produced by methods analogousto known methods. Applicable methods in this respect are described forexamples at the following places in the literature: J. Org. Chem. 30,4104 (1965); Tetrahedron 1967, 487; Tetrahedron 1967, 493; Org.Syntheses III, 650; Org. Syntheses III, 652; Org. Syntheses III, 710;and J. Org. Chem. 34, 3430 (1969).

Reference may be made in detail to some methods of production ofstarting materials. Thus, the starting materials for compounds of theformula I wherein R₃ is an N₃ group can be produced as follows:

nitration of compounds of the formula VIII with a reactive nitratingreagent to give compounds of the formula IX, and subsequenthydrogenation of the nitro compounds with a customary hydrogenatingagent to obtain compounds of the formula VI: ##STR24##

The compounds of the formula I contain in the molecule moiety Y at leastone asymmetrical carbon atom. Racemates which are produced can be splitinto the optical antipodes by known methods of splitting racemates. Theoptical antipodes of the formula I have varying microbicidal activities.

There can be present depending on the manner of substitution furtherasymmetrical carbon atoms in the molecule of the compounds of theformula I.

Independently of the described optical isomerism in the compounds of theformula I, there is observed an atropisomerism around the aryl--N< axis.

When no specific synthesis is carried out to isolate pure isomers, aproduct of the formula I is usually obtained as a mixture of thesepossible isomers.

It has been found that compounds of the formula I surprisingly exhibit avery favourable microbicidal spectrum for practical requirements. Theycan be used for example to protect cultivated plants.

The main field of application for compounds of the formula I is thecombating of harmful microorganisms, particularly phytopathogenic fungi.The compounds of the formula I thus have for practical purposes a veryfavourable curative, preventive and systemic action for the protectionof cultivated plants, without these becoming impaired as a result ofundesirable side-effects. Cultivated plants within the scope of thepresent invention are for example: cereals (wheat, barley, rye, oats andrice); beet: (sugar beet and fodder beet); pomaceous fruit, stone fruitand soft fruit: (apples, pears, plums, peaches, almonds, cherries,strawberries, rasberries and blackberries); legumes: (beans, lentils,peas and soya-bean); oil plants: (rape, mustard, poppy, olives,sunflowers, coco, castor-oil plants, cocoa and groundnuts);Cucurbitacea: (pumpkins, cucumbers and melons); fibre plants: (cotton,flax, hemp and jute); citrus fruits: (oranges, lemons, grapefruit andmandarins); varieties of vegetables: (spinach, lettuce, asparagus,varieties of cabbage, carrots, onions, tomatoes, potatoes and paprika);or plants such as maize, tobacco, nuts, coffee, sugar beet, tea,grapevines, hops, bananas and natural rubber plants; and also ornamentalplants.

Microorganisms occurring on plants or on parts of plants (fruit,blossom, foliage, stalks, tubers or roots) of the said crops and ofrelated cultivated crops can be inhibited or destroyed with the activesubstances of the formula I, and also parts of plants subsequentlygrowing remain preserved from such microorganisms. The active substancesare effective against the phytopathogenic fungi belonging to thefollowing classes: against the Peronosporales (Phytophthora, Pythium andPlasmopara) belonging to the Oomycetes class, and also against theAscomycetes, such as Erysiphe and Venturia pathogens.

Furthermore, the compounds of the formula I have a systemic action. Theycan also be used as dressing agents for the treatment of seed (fruits,tubers and grain), and of plant cuttings to protect them from fungusinfections, and also against phytopathogenic fungi occurring in thesoil.

The invention relates therefore also to the use of the compounds of theformula I for combating phytopathogenic microorganisms and/or forpreventing infection on plants.

The compounds of the formula I are used either in an unmodified form orpreferably together with auxiliaries customarily employed in formulationpractice, and are thus processed in a known manner for example into theform of emulsion concentrates, directly sprayable or dilutablesolutions, diluted emulsions, wettable powders, soluble powders, dustsor granulates, and also encapsulations in for example polymericsubstances. The application processes, such as spraying, atomising,dusting, scattering or pouring, and likewise the type of composition,are selected to suit the objectives to be achieved and the givenconditions.

Active substances of the formula I can be applied, simultaneously orsuccessively, with further active substances to the surface or plant tobe treated. These active substances can be fertilisers, trace-elementagents or other preparations influencing plant growth. They can howeveralso be selective herbicides, insecticides, fungicides, bactericides,nematocides or molluscicides, or mixtures of several of thesepreparations, optionally together with carriers, surface-active agentsor additives facilitating application, which are customarily used informulation practice.

The formulations, that is to say, the compositions or preparationscontaining the active substance of the formula I and optionally a solidor liquid additive, are produced in a known manner, for example by theintimate mixing and/or grinding of the active substances with extenders,such as with solvents, solid carriers and optionally surface-activecompounds (tensides).

Suitable carriers and additives can be solid and liquid and correspondto the substances commonly used in formulation practice, such as naturalor regenerated mineral substances, solvents, dispersing agents, wettingagents, adhesives, thickeners, binders or fertilisers.

Suitable solvents are: aromatic hydrocarbons preferably the fractions C₈to C₁₂, such as xylene mixtures or substituted naphthalenes, phthalicesters, such as dibutyl or dioctylphthalate, aliphatic hydrocarbons,such as cyclohexane or paraffins, alcohols and glycols, as well asethers and esters thereof, such as ethanol, ethylene glycol, ethyleneglycol monomethyl or -ethyl ethers, ketones such as cylohexanone,strongly polar solvents, such as N-methyl-2-pyrrolidone,dimethylsulfoxide or dimethylformamide, as well as optionally epoxidisedvegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, for example for dusts and dispersible powders,are as a rule natural mineral fillers, such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties, it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers.

The surface-active agents (tensides) commonly used in formulationpractice are described, inter alia, in the following publications: "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp.,Ringwood, N.J., 1980; and Sisely and Wood, "Encyclopedia of SurfaceActive Agents", Chemical Publishing Co., Inc. New York, 1980.

The pesticidal preparations contain as a rule 0.1 to 99, particularly0.1 to 95%, by weight of active substance of the formula I, 1 to 99% byweight of a solid or liquid additive, and 0 to 25, especially 0.1 to25%, by weight of a surface-active agent.

Whereas commercial products are preferably in the form of concentratedcompositions, the compositions employed by the end-user are as a rulediluted.

The compositions can also contain further additives, such asstabilisers, antifoaming agents, viscosity regulators, binders andadhesives, as well as fertilisers, or other active substances forobtained special effects.

The invention relates also to compositions containing, as at least oneactive substance, a compound of the formula I, and to the use of thecompositions for combating and/or preventing infestation by harmfulmicroorganisms. The present invention embraces also the production ofthe compositions, this being characterised by the intimate mixing of theactive substance with one or more of the substances or groups ofsubstances described herein. Included also is a method of combatingharmful microorganisms, which method comprises the application of thecompounds of the formula I or of the novel compositions containing them.

The following Examples serve to further illustrate the presentinvention, without limiting the scope thereof. The temperature valuesare given in degrees Centigrade; and percentages and parts relate toweight. Except where otherwise stated, the isomeric mixture is meant inall cases where an active substance of the formula I is referred to.

EXAMPLE 1 Production of ##STR25##N-(1'-Methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-acetoxymethylaniline

35.0 g ofN-(1'-methoxycarbonyl-ethyl)-2,6-dimethyl-3-acetoxymethylaniline and13.3 g of sodium carbonate were placed into 250 ml of toluene, and 20.0g of methoxyacetic acid chloride, dissolved in 50 ml of toluene, wereslowly added. After the exothermic reaction had subsided, thetemperature was held at 45° C. for 7 hours by means of a water-bath. Thecooled reaction mixture was filtered, and the filtrate was concentratedin a rotary evaporator. The oily residue was distilled: b.p. 167°-171°C. at 0.07 bar.

EXAMPLE 2 Production of ##STR26##N-(1'-Methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-hydroxymethylaniline

23.0 g ofN-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-acetoxymethylaniline,9.2 g of 30% sodium hydroxide solution and 100 ml of acetone werestirred for 3 hours at room temperature; 20 ml of water were then added,and the reaction mixture was extracted twice with 50 ml of diethyl ethereach time. The combined ether extracts were dried over sodium sulfate,and the solvent was evaporated off. The oily crude product waschromatographed through a silica gel column by means of ether/chloroform(1:1) to thus obtain the product in the form of colourless oil: n_(D) ¹⁴=1.5352.

EXAMPLE 3 Production of ##STR27##N-(1'-Methoxycarbonyl-ethyl)-N-methoxyacetyl-2-methyl-6-azidoaniline

10.0 g ofN-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2-methyl-6-aminoanilinewere strirred up with 75 g of ice and 15 ml of conc. hydrochloric acidat 0° to 5° C. until a clear solution was formed. At 0° to 5° C. wherethen added dropwise, within 10 minutes, 2.5 g of sodium nitritedissolved in 10 ml of water. The reddish-brown solution was stirred fora further 30 minutes at the above temperature, and 100 ml of ether weresubsequently added. There was thereupon added dropwise at 0° to 5° C.,within 15 minutes, a solution of 2.5 g of sodium azide in 10 ml ofwater, and the temperature was allowed to rise in the course of 30minutes to room temperature. The reaction mixture was extracted withether; the organic phase was then washed with sodium hydrogencarbonate/water, dried with magnesium sulfate, and the solvent wasevaporated off. The resulting oil was dried at 40° C. in vacuo; n_(D) ²⁶: 1.5396. n_(D) ²⁸.5 : 1.5389.

EXAMPLE 4 Production of ##STR28##N-(1'-Methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-(3',5'-dichlorophenylcarbamoylmethyl)-aniline

16.2 g ofN-(1'-methoxycarbonyl-ethyl)-2,6-dimethyl-3-(3',5'-dichlorophenylcarbamoylmethyl)-anilineand 3.2 g of pyridine were placed into 120 ml of toluene; and within 15minutes were added 4.7 g of methoxyacetic acid chloride, dissolved in 30ml of toluene. After the exothermic reaction had subsided, stirring wasmaintained for 4 hours at room temperature, and the reaction suspensionwas then filtered with suction. The yellow filtrate was washed withwater, dried over sodium sulfate, and concentrated in a rotaryevaporator. The solid residue was digested with ether, and the whitecrystals were filtered off with suction; m.p. 126°-128° C.

The following compounds of the formula I were produced in a manneranalogous to that described in the foregoing.

                                      TABLE 1.1                                   __________________________________________________________________________    Compounds of the formula                                                       ##STR29##                                                                    Comp.                                                                         No.  R.sub.1      R.sub.2.sup.'                                                                     R.sub.3.sup.'                                                                              R.sub.6.sup.'                                                                       Y            Physical                __________________________________________________________________________                                                          data                    1.1.1.                                                                             CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OCOCH.sub.3                                                                       CH.sub.3                                                                             ##STR30##   b.p.                                                                          167-171° C.                                                            0.07 mbar               1.1.2.                                                                             CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OH  CH.sub.3                                                                             ##STR31##   n.sub.D.sup.14  =                                                             1.5352                  1.1.3.                                                                             CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          H            N.sub.3                                                                              ##STR32##   n.sub.D.sup.28.5 =                                                            1.5389                  1.1.4.                                                                             CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                           ##STR33##   CH.sub.3                                                                             ##STR34##   m.p.                                                                          126-128° C.      1.1.5.                                                                             CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR35##   m.p. 99-118°                                                           C.                      1.1.6.                                                                             CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          H            CH.sub.2 OH                                                                          ##STR36##   viscous oil             1.1.7.                                                                              ##STR37##   CH.sub.3                                                                          CH.sub.2 OCOCH.sub.3                                                                       CH.sub.3                                                                             ##STR38##   viscous oil             1.1.8.                                                                             CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                           ##STR39##   CH.sub.3                                                                             ##STR40##   viscous oil             1.1.9.                                                                             CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OCOOCH.sub.3                                                                      CH.sub.3                                                                             ##STR41##   n.sub.D.sup.14 =                                                              1.5172                  1.1.10.                                                                             ##STR42##   CH.sub.3                                                                          CH.sub.2 OH  CH.sub.3                                                                             ##STR43##   oil                     1.1.11.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3     N.sub.3                                                                              ##STR44##   m.p. 80-82°                                                            C.                      1.1.12.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR45##   m.p. 88-93°                                                            C.                      1.1.13.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          H            N.sub.3                                                                              ##STR46##                           1.1.14.                                                                             ##STR47##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR48##   oil                     1.1.15.                                                                             ##STR49##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR50##                           1.1.16.                                                                             ##STR51##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR52##                           1.1.17.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      OCH.sub.3                                                                            ##STR53##                           1.1.18.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR54##                           1.1.19.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          H            N.sub.3                                                                              ##STR55##   yellow oil              1.1.20.                                                                             ##STR56##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR57##                           1.1.21.                                                                             ##STR58##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR59##                           1.1.22.                                                                             ##STR60##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR61##                           1.1.23.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      OCH.sub.3                                                                            ##STR62##                           1.1.24.                                                                            CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                         N.sub.3      OCH.sub.3                                                                            ##STR63##                           1.1.25.                                                                             ##STR64##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR65##                           1.1.26.                                                                             ##STR66##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR67##                           1.1.27.                                                                            CHCH.sub.2   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR68##                           1.1.28.                                                                             ##STR69##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR70##                           1.1.29.                                                                             ##STR71##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR72##                           1.1.30.                                                                             ##STR73##   CH.sub.3                                                                          N.sub.3      OCH.sub.3                                                                            ##STR74##                           1.1.31.                                                                             ##STR75##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR76##                           1.1.32.                                                                             ##STR77##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR78##                           1.1.33.                                                                             ##STR79##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR80##                           1.1.34.                                                                             ##STR81##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR82##   m.p. 87-92°                                                            C.                      1.1.35.                                                                             ##STR83##   CH.sub.3                                                                          H            N.sub.3                                                                              ##STR84##                           1.1.36.                                                                             ##STR85##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR86##                           1.1.37.                                                                             ##STR87##   CH.sub.3                                                                          CH.sub.2 OCOCH.sub.3                                                                       CH.sub.3                                                                             ##STR88##                           1.1.38.                                                                            CH.sub.2 SO.sub.2 CH.sub.3                                                                 CH.sub.3                                                                          CH.sub.2 OCOCH.sub.3                                                                       CH.sub.3                                                                             ##STR89##                           1.1.39.                                                                            CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.3                                                                          H            N.sub.3                                                                              ##STR90##                           1.1.40.                                                                             ##STR91##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR92##                           1.1.41.                                                                             ##STR93##   CH.sub.3                                                                          CH.sub.2 OCOCH.sub.3                                                                       CH.sub.3                                                                             ##STR94##                           1.1.42.                                                                            CH.sub.2 OCH.sub.2CHCH.sub.2                                                               CH.sub.3                                                                          CH.sub.2 OCOCH.sub.3                                                                       CH.sub.3                                                                             ##STR95##                           1.1.43.                                                                            CH.sub.2 OCH.sub.2CHCH.sub.2                                                               CH.sub.3                                                                          H            N.sub.3                                                                              ##STR96##                           1.1.44.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR97##                           1.1.45.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3     N.sub.3                                                                              ##STR98##                           1.1.46.                                                                             ##STR99##   CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR100##  m.p.                                                                          117-120° C.      1.1.47.                                                                            CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR101##                          1.1.48.                                                                            CH.sub.2 OCH.sub.3                                                                         Cl  H            N.sub.3                                                                              ##STR102##                          1.1.49.                                                                             ##STR103##  CH.sub.3                                                                          CH.sub.3     N.sub.3                                                                              ##STR104##                          1.1.50.                                                                             ##STR105##  CH.sub.3                                                                          CH.sub.3     N.sub.3                                                                              ##STR106##                          1.1.51.                                                                             ##STR107##  CH.sub.3                                                                          H            N.sub.3                                                                              ##STR108##                          1.1.52.                                                                             ##STR109##  CH.sub.3                                                                          H            N.sub.3                                                                              ##STR110##                          1.1.53.                                                                            CH.sub.2 CH.sub.2 OCH.sub.3                                                                CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR111##                          1.1.54.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          H            N.sub.3                                                                              ##STR112##                          1.1.55.                                                                             ##STR113##  CH.sub.3                                                                          H            N.sub.3                                                                              ##STR114##                          1.1.56.                                                                             ##STR115##  CH.sub.3                                                                          H            N.sub.3                                                                              ##STR116##                          1.1.57.                                                                             ##STR117##  CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR118##                          1.1.58.                                                                            CH.sub.2 OCOCH.sub.3                                                                       CH.sub.3                                                                          H            N.sub.3                                                                              ##STR119##                          1.1.59.                                                                            CH.sub.2 CH.sub.2 OCH.sub.3                                                                CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR120##                          1.1.60.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR121##                          1.1.61.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR122##                          1.1.62.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          H            N.sub.3                                                                              ##STR123##                          1.1.63.                                                                             ##STR124##  CH.sub.3                                                                          H            N.sub.3                                                                              ##STR125##                          1.1.64.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          H            N.sub.3                                                                             CH.sub.2CCH                          1.1.65.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                            CH.sub.3CCJ                          1.1.66.                                                                             ##STR126##  CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR127##                          1.1.67.                                                                            CHCHCH.sub.3 CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                             ##STR128##                          1.1.68.                                                                             ##STR129##  CH.sub.3                                                                          N.sub.3      CH.sub.3                                                                            CH.sub.2CCH.sub.3                    1.1.69.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OH  CH.sub.3                                                                             ##STR130##                          1.1.70.                                                                            CH.sub.2 OC.sub.2 H.sub.5                                                                  CH.sub.3                                                                          CH.sub.2 OH  CH.sub.3                                                                             ##STR131##                          1.1.71.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OH  CH.sub.3                                                                             ##STR132##                          1.1.72.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3     CH.sub.2 OH                                                                          ##STR133##                          1.1.73.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OH  CH.sub.3                                                                             ##STR134##                          1.1.74.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OH  CH.sub.3                                                                             ##STR135##                          1.1.75.                                                                            CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OH  CH.sub.3                                                                             ##STR136##                          1.1.76.                                                                            CH.sub.2 OCH.sub.3                                                                         Cl  H            CH.sub.2 OH                                                                          ##STR137##                      

    TABLE 1.2                                                                     __________________________________________________________________________    Compounds of the formula:                                                      ##STR138##                                                                   Comp.                                       Physical                          No. R.sub.1  R.sub.2 '                                                                         R.sub.3 '                                                                         R.sub.4 '                                                                        R.sub.5 '                                                                         R.sub.6 '                                                                         Y           data                              __________________________________________________________________________    1.2.1.                                                                            CH.sub.2 OCH.sub.3                                                                     CH.sub.3                                                                          CH.sub.3                                                                          N.sub.3                                                                          CH.sub.3                                                                          CH.sub.2                                                                           ##STR139##                                   1.2.2.                                                                            CH.sub.2 Oi-C.sub.3 H.sub.7                                                            CH.sub.3                                                                          CH.sub.3                                                                          N.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                           ##STR140##                                   1.2.3.                                                                            CH.sub.2 OCH.sub.3                                                                     CH.sub.3                                                                          CH.sub.3                                                                          N.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                           ##STR141##                                   1.2.4.                                                                             ##STR142##                                                                            CH.sub.3                                                                          CH.sub.3                                                                          N.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                           ##STR143##                                   1.2.5.                                                                            CH.sub.2 SO.sub.2 CH.sub.3                                                             CH.sub.3                                                                          CH.sub.3                                                                          N.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                           ##STR144##                                   __________________________________________________________________________

                  TABLE 2.1                                                       ______________________________________                                        Compounds of the formula                                                       ##STR145##                                                                   R.sub.4 ' = H                                                                                                        Phys-                                  Comp.                                  ical                                   No.   R.sub.3 '    R.sub.5 '                                                                             Y           data                                   ______________________________________                                        2.1.1.                                                                              N.sub.3      H                                                                                      ##STR146## resin                                  2.1.2.                                                                              CH.sub.3     N.sub.3                                                                                ##STR147##                                        2.1.3.                                                                              N.sub.3      H                                                                                      ##STR148##                                        2.1.4.                                                                              CH.sub.2 OH  H                                                                                      ##STR149##                                        2.1.5.                                                                              CH.sub.3     N.sub.3                                                                                ##STR150##                                        2.1.6.                                                                              N.sub.3      H                                                                                      ##STR151##                                        2.1.7.                                                                              CH.sub.3     N.sub.3                                                                                ##STR152##                                        2.1.8.                                                                              CH.sub.2 OCOCH.sub.3                                                                       NO.sub.2                                                                               ##STR153##                                        2.1.9.                                                                              CH.sub.3     N.sub.3                                                                                ##STR154##                                         2.1.10.                                                                            N.sub.3      H                                                                                      ##STR155##                                        ______________________________________                                    

                  TABLE 2.2                                                       ______________________________________                                        Compounds of the formula                                                       ##STR156##                                                                   Comp.                                                                         No.        Y              Physical data                                       ______________________________________                                        2.2.1.                                                                                    ##STR157##                                                        2.2.2.                                                                                    ##STR158##    m.p. 45-57° C.                               2.2.3.                                                                                    ##STR159##                                                        2.2.4.                                                                                    ##STR160##                                                        2.2.5.                                                                                    ##STR161##                                                        2.2.6.                                                                                    ##STR162##                                                        2.2.7.                                                                                    ##STR163##                                                        ______________________________________                                    

                  TABLE 2.3                                                       ______________________________________                                        Compounds of the formula                                                       ##STR164##                                                                   Comp.                                                                         No.      R.sub.1         Physical data                                        ______________________________________                                        2.3.1.   CH.sub.2 OC.sub.2 H.sub.5                                                                     m.p. 93-96° C.                                2.3.2.                                                                                  ##STR165##                                                          2.3.3.                                                                                  ##STR166##                                                          2.3.4.                                                                                  ##STR167##                                                          2.3.5.   CH.sub.2 OSO.sub.2 NHCH.sub.3                                        2.3.6.   CH.sub.2 SO.sub.2 CH.sub.3                                           2.3.7.   CH.sub.2 CH.sub.2 OCH.sub.3                                          ______________________________________                                    

                  TABLE 2.4                                                       ______________________________________                                        Compounds of the formula                                                       ##STR168##                                                                   Comp. No.  Y'            Physical data                                        ______________________________________                                        2.4.1.     CH.sub.2 CN   wax-like substance                                   2.4.2.     CH.sub.2 CH(OCH.sub.3).sub.2                                                                viscous oil                                          2.4.3.     CH.sub.2 C CH m.p. 57-63° C.                                ______________________________________                                    

BIOLOGICAL EXAMPLES

The compositions used in the following Examples are formulated in themanner described in the subsequent formulation examples.

EXAMPLE 5 Action against Phytophthora infestans on tomato plants

(a) Residual protective action

After 3-weeks' cultivation, tomato plants were sprayed with a sprayliquor produced from wettable powder of the active substance (0.02% ofactive substance). After 24 hours, the treated plants were infested witha suspension of sporangia of the fungus. An assessment of the fungusinfection was made after incubation of the infested plants during 5 daysat 20° l C. with 90-100% relative humidity.

Compared with the fungus infection occurring on the control plants (100%infection), the infection on tomato plants treated with any one of thecompounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.4, 1.1.5, 1.1.7, 1.1.9, 1.1.10,1.1.12, 1.1.14, 1.1.19, 1.1.34, 1.1.61 and 1.1.62, and Nos. 2.2.1, 2.2.2and 2.2.3 was reduced to less than 10%.

(b) Systemic action

A spray liquor prepared from wettable powder of the active substance(0.006% of active substance, relative to the volume of soil) was appliedto the soil in which tomato plants had been cultivated for 3 weeks. Carewas taken to ensure that the spray liquor did not come into contact withthe parts of the plants above the soil. After 48 hours, the treatedplants were infested with a suspension of sporangia of the fungus. Anassessment of fungus infection was made after incubation of the infestedplants during 5 days at 20° C. with 90-100% relative humidity.

Compounds exhibiting in the above test a very good systemic action were,inter alia: Compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.5, 1.1.9, 1.1.10,1.1.12, 1.1.14, 1.1.19, 1.1.34, 1.1.54 and 1.1.61, and also No. 2.2.1and No. 2.2.2. Compared with fungus infection occuring on the untreatedbut infested control plants (100% infection), the infection on tomatoplants treated with any one of the these compounds had been almostcompletely eliminated (0 to 5%).

(c) Residual curative action

After 3-weeks' cultivation, tomato plants were infested with asuspension of sporangia of the fungus. After an incubation time of 22hours in a moist chamber at 20° C. with 90°-100° relative humidity, theinfested plants were dried, and then sprayed with a spray liquorprepared from wettable powder of the active substance (0.06% of activesubstance). After the drying of the applied coating, the treated plantswere returned to the moist chamber. An assessment of fungus infectionwas made 5 days after infestation.

Compared with fungus infection occurring on the untreated but infestedcontrol plants (100% infection), the infection on tomato plants treatedwith any one of the Compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.10, 1.1.12,1.1.14, 1.1.19, 1.1.34 and 1.1.61 and Nos. 2.2.1, 2.2.2 and 2.2.3 wasless than 10%.

EXAMPLE 6 Residual protective action against Venturia inaequalis onapple shoots

Apple seedlings having 10-20 cm long fresh shoots were sprayed with aspray liquor prepared from wettable powder of the active substance(0.06% of active substance). The treated plants were sprayed after 24hours with a conidiospore suspension of the fungus. The plants were thenincubated for 5 days with 90-100% relative humidity, and for a further10 days they were kept at 20°-24° C. in a greenhouse. The extent of scabinfection was assessed 15 days after infestation. The occurrence of thedisease was reduced to 10 to 15% by, inter alia: the compounds Nos.1.1.1, 1.1.2, 1.1.10, 1.1.37, 1.1.42, 1.1.69, 2.1.1, 2.1.4 and 2.1.8.

EXAMPLE 7 Action against Pythium debaryanum on sugar beet plants

(a) Effect after soil application

The fungus was cultivated on a carrot-chips nutrient solution, and wasthen added to a soil/sand mixture. The soil infested in this manner wasplaced into flower pots, and sown with sugar-beet seeds. Immediatelyafter the sowing, the test preparation prepared from wettable powder waspoured, as an aqueous suspension, over the soil (20 ppm of any one ofthe compounds in the Tables 1 and 2, relative to the volume of soil).The pots were then placed for 2-3 weeks in a greenhouse at about 20° C.The soil was maintained during this period uniformly moist by lightwatering. In the evaluation of the test, the sprouting of the sugar-beetplants and the proportion of healthy plants and of diseased plants wereassessed.

(b) Effect after dressing application

The fungus was cultivated on a carrot-chips nutrient solution, andapplied to a soil/sand mixture. The soil infested in this manner wasplaced into soil trays, and sown with sugar-beet seeds which had beendressed with the test preparations formulated as dressing powder (0.06%of any one of the compounds in Tables 1 and 2). The sown trays were leftfor 2-3 weeks in a greenhouse at about 20° C. The soil was maintaineduniformly moist by light spraying. In the assessment of the testresults, the extent of sprouting of the sugar-beet plants wasdetermined.

The compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.5, 1.1.7, 1.1.9, 1.1.10,1.1.12, 1.1.14, 1.1.19, 1.1.25, 1.1.34, 1.1.54, 1.1.61 and 1.1.62 andNos. 2.2.1, 2.2.2 and 2.2.3 were completely effective against Pythiumpathogens (over 90% of plants had sprouted) in both tests (a) and (b).The plants had a healthy appearance.

An equally good effect was achieved in analogous tests against Phythiumpathogens on maize plants.

EXAMPLE 8 Action against Podosphaera leucotricha on apple seedlings

Residual protective action

Apple seedlings having about 5 developed leaves were sprayed with aspray liquor prepared from wettable powder of the active substance(0.06% of active substance). After 24 hours, the treated plants wereinfested with a conidiospore suspension of the fungus, and weretransferred to a controlled atmosphere chamber at 20° with 70% relativehumidity. The assessment of fungus infection was made 12 days afterinfestation.

Compared with fungus infection occurring on the untreated but infestedapple seedlings (100% infection), the infection on apple seedlingstreated with any one of the compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.4,1.1.5, 1.1.7, 1.1.9, 1.1.10, 1.1.14, 1.1.19, 1.1.25, 1.1.34, 1.1.54,1.1.61, and 1.1.62 and Nos. 2.2.1, 2.2.2 and 2.2.3 was less than 10%.

Formulation examples for liquid active substances of the formula I(%=percent by weight) EXAMPLE 9

    ______________________________________                                        Emulsion concentrates                                                                            (a)      (b)    (c)                                        ______________________________________                                        active substance   25%      40%    50%                                        from Tables 1.1-2.4                                                           calcium dodecylbenzenesulfonate                                                                   5%       8%     6%                                        castor oil-polyethylene glycol                                                                    5%      --     --                                         ether (36 mols of ethylene oxide)                                             tributylphenol-polyethylene glycol                                                               --       12%     4%                                        ether (30 mols of ethylene oxide)                                             cyclohexanone      --       15%    20%                                        xylene mixture     65%      25%     20%.                                      ______________________________________                                    

Emulsions of any required concentration can be produced from suchconcentrates by dilution with water.

EXAMPLE 10

    ______________________________________                                        Solutions          (a)     (b)    (c)   (d)                                   ______________________________________                                        active substance   80%     10%    5%    95%                                   from Tables 1.1-2.4                                                           ethylene glycol-monomethyl ether                                                                 20%     --     --    --                                    polyethylene glycol M G 400                                                                      --      70%    --    --                                    N--methyl-2-pyrrolidone                                                                          --      20%    --    --                                    epoxidised coconut oil                                                                           --      --     1%     5%                                   ligroin (boiling limits 160-190° C.)                                                      --      --     94%    --.                                  ______________________________________                                    

The solutions are suitable for application in the form of very finedrops.

EXAMPLE 11

    ______________________________________                                        Granulates             (a)     (b)                                            ______________________________________                                        active substance from Tables 1.1-2.4                                                                 5%      10%                                            kaolin                 94%     --                                             highly dispersed silicic acid                                                                        1%      --                                             attapulgite            --       90%.                                          ______________________________________                                    

The active substance is dissolved in methylene chloride, the solution issprayed onto the carrier, and the solvent is subsequently evaporated offin vacuo.

EXAMPLE 12

    ______________________________________                                        Dusts                  (a)     (b)                                            ______________________________________                                        active substance from Tables 1.1-2.4                                                                 2%      5%                                             highly dispersed silicic acid                                                                        1%      5%                                             talcum                 97%     --                                             kaolin                 --      90%.                                           ______________________________________                                    

Ready-for-use dusts are obtained by the intimate mixing together of thecarriers with the active substance.

Formulation examples for solid active substances of the formula I(%=percent by weight) EXAMPLE 13

    ______________________________________                                        Wettable powders     (a)      (b)     (c)                                     ______________________________________                                        active substance from Tables 1.1-2.4                                                               25%      50%     75%                                     sodium lignin sulfonate                                                                            5%        5%     --                                      sodium lauryl sulfate                                                                              3%       --       5%                                     sodium diisobutylnaphthalene sulfonate                                                             --        6%     10%                                     octylphenolpolyethylene glycol ether                                                               --        2%     --                                      (7-8 mols of ethylene oxide)                                                  highly dispersed silicic acid                                                                      5%       10%     10%                                     kaolin               62%      27%     --                                      ______________________________________                                    

The active substance is well mixed with the additives and the mixture isthoroughly ground in a suitable mill. Wettable powders which can bediluted with water to give suspensions of the required concentration areobtained.

EXAMPLE 14

    ______________________________________                                        Emulsion concentrate                                                          ______________________________________                                        active substance from Tables 1.1-2.4                                                                 10%                                                    octylphenolpolyethylene glycol ether                                                                  3%                                                    (4-5 mols of ethylene oxide)                                                  calcium dodecylbenzenesulfonate                                                                       3%                                                    castor oil polyglycol ether                                                                           4%                                                    (36 mols of ethylene oxide)                                                   cyclohexanone          30%                                                    xylene mixture          50%.                                                  ______________________________________                                    

Emulsions of the required concentration can be obtained from thisconcentrate by dilution with water.

EXAMPLE 15

    ______________________________________                                        Dusts                   (a)    (b)                                            ______________________________________                                        active substance from Tables 1.1-2.4                                                                   5%     8%                                            talcum                  95%    --                                             kaolin                  --      92%.                                          ______________________________________                                    

Dusts ready for use are obtained by mixing the active substance with thecarriers and grinding the mixture in a suitable mill.

EXAMPLE 16

    ______________________________________                                        Extruder granulate                                                            ______________________________________                                        active substance from Tables 1.1-2.4                                                                 10%                                                    sodium lignin sulfonate                                                                               2%                                                    carboxymethylcellulose  1%                                                    kaolin                  87%.                                                  ______________________________________                                    

The active substance is mixed and ground with the additives, and themixture is moistened with water. This mixture is then extruded and driedin a stream of air.

EXAMPLE 17

    ______________________________________                                        Coated granulate                                                              ______________________________________                                        active substance from Tables 1.1-2.4                                                                 3%                                                     polyethylene glycol (MG 200)                                                                         3%                                                     kaolin                 94%.                                                   ______________________________________                                    

The finely ground acitve substance is evenly applied, in a mixer, to thekaolin moistened with polyethylene glycol. Dustfree coated granules areobtained in this manner.

EXAMPLE 18

    ______________________________________                                        Suspension concentrate                                                        ______________________________________                                        active substance from Tables 1.1-2.4                                                                 40%                                                    ethylene glycol        10%                                                    nonylphenolpolyethylene glycol                                                                        6%                                                    ether (15 mols of ethylene oxide)                                             sodium lignin sulfonate                                                                              10%                                                    carboxymethyl cellulose                                                                               1%                                                    37% aqueous formaldehyde solution                                                                    0.2%                                                   silicone oil in the form of a                                                                        0.8%                                                   75% aqueous emulsion                                                          water                   32%.                                                  ______________________________________                                    

The finely ground active substance is intimately mixed with theadditives. There is thus obtained a suspension concentrate from whichcan be prepared, by dilution with water, suspensions of theconcentration required.

What is claimed is:
 1. A compound of the formula I ##STR169## wherein Aris a group of the formula ##STR170## R₁ is 2-furyl, 2-tetrahydrofuryl,C₂ -C₄ -alkenyl, cyclopropyl, β-(C₁ -C₄)-alkoxyethyl or --CH₂ Z, eachbeing unsubstituted or substituted by halogen, and Z being(a) --OH, (b)-1H-1,2,4-triazolyl, 1-imidazolyl or 1-pyrazolyl, (c) --S(O)_(n) --R₁₃where R₁₃ is C₁ -C₄ -alkyl, and n is 1 or 2, (d) --X--R₁₄ where X isoxygen or sulfur, and R₁₄ is C₁ -C₆ -alkyl, C₃ -C₄ -alkenyl or C₃ -C₄-alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy, (e)--OSO₂ --R₁₅ where R₁₅ is C₁ -C₄ -alkyl, or mono- or di-(C₁-C₃)-alkylamine, (f) ##STR171## where X is oxygen or sulfur, R₁₆ is C₁-C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, and R₁₇ is C₁ -C₄-alkoxy or C₁ -C₄ -alkylamino, or (g) ##STR172## where R₁₈ is C₁ -C₃-alkyl which is unsubstituted or substituted by C₁ -C₂ -alkoxy, R₂ is C₁-C₃ -alkyl, C₁ -C₃ -alkoxy or halogen, R₃ is --CH₂ OH, --N₃, ##STR173##where R' is C₁ -C₆ -alkyl or C₂ -C₄ -alkenyl, each unsubstituted orsubstituted by halogen or C₁ -C₃ -alkoxy, or it is unsubstituted orphenyl substituted by chlorine, and X is oxygen or sulfur, R₄ ishydrogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, halogen, --NO₂ or --NH₂, R₅ ishydrogen or C₁ -C₃ -alkyl, R₆ is hydrogen or C₁ -C₃ -alkyl, R₇ ishydrogen, or C₁ -C₂ -alkyl which is unsubstituted or substituted byhalogen, --OH, --OC₁ --C₃ -alkyl or ##STR174## R₈ is C₁ -C₄ -alkyl whichis unsubstituted or substituted by C₁ -C₂ -alkoxy, X is oxygen orsulfur.
 2. A compound according to claim 1, whereinR₁ is 2-furyl,2-tetrahydrofuryl, C₂ -C₄ -alkenyl, cyclopropyl, β-(C₁ -C₂)-alkoxyethylor CH₂ --Z, where Z is(a) --OH, (b) 1H-1,2,4-triazolyl or 1-imidazolyl,(c) --S(O)_(n) --R₁₃ where R₁₃ is C₁ -C₂ -alkyl, and n is 2, (d)--X'--R₁₄ where X' is oxygen or sulfur, and R₁₄ is C₁ -C₆ -alkyl, C₃ -C₄-alkenyl or C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂-alkoxy, (e) --OSO₂ --R₁₅ where R₁₅ is C₁ -C₂ -alkyl, or mono- or di-(C₁-C₂)-alkylamine, (f) ##STR175## where X" is sulfur, R₁₆ is C₁ -C₂-alkyl, C₁ -C₄ -alkoxy or C₁ -C₂ -alkylamino, and R₁₇ is C₁ -C₄ -alkoxyor C₁ -C₄ -alkylamino, or (g) ##STR176## where R₁₈ is C₁ -C₂ -alkylwhich is unsubstituted or substituted by C₁ -C₂ -alkoxy, R₂ is C₁ -C₂-alkyl, C₁ -C₂ -alkoxy or halogen, R₃ is --CH₂ OH, --N₃, ##STR177##where R' is C₁ -C₃ -alkyl or C₂ -C₃ -alkenyl, each unsubstituted orsubstituted by chlorine or methoxy, and X'" is oxygen or sulfur, R₄ ishydrogen, C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy, --NO₂ or --NH₂, R₅ is hydrogenor C₁ -C₂ -alkyl, R₆ is hydrogen or C₁ -C₂ -alkyl, R₇ is hydrogen, or C₁-C₂ -alkyl which is unsubstituted or substituted by halogen, --OH,--O(C₁ -C₂)-alkyl or ##STR178## R₈ is C₁ -C₃ -alkyl which isunsubstituted or substituted by C₁ -C₂ -alkoxy.
 3. A compound accordingto claim 2, whereinR₁ is 2-furyl, 2-tetrahydrofuryl, C₂ -C₄ -alkenyl,cyclopropyl, 4-methoxyethyl or --CH₂ Z, where Z is(a)1H-1,2,4-triazolyl, (b) --S(O)_(n) --R₁₃ where R₁₃ is CH₃, and n is 2,(c) --X'^(v) --R₁₄ where X'^(v) is oxygen, and R₁₄ is C₁ -C₄ -alkyl, C₃-C₄ -alkenyl or C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁-C₂ -alkoxy, (d) --OSO₂ --R₁₅ where R₁₅ is mono-(C₁ -C₃)-alkylamine, (e)##STR179## where X^(v) is sulfur, and R₁₆ and R₁₇ independently of oneanother are each C₁ -C₃ -alkoxy, or (f) ##STR180## where R₁₈ is C₁ -C₃-alkyl, R₂ is methyl, methoxy or chlorine, R₃ is --CH₂ OH, --N₃ or##STR181## R₄ is hydrogen, methyl, methoxy, NO₂ or NH₂, R₅ is hydrogenor methyl, R₆ is hydrogen or methyl, R₇ is C₁ -C₂ -alkyl which isunsubstituted or substituted by chlorine, --OH, --OC₁ --C₂ -alkyl or##STR182## R₈ is C₁ -C₃ -alkyl X is oxygen.
 4. A compound according toclaim 3, whereinR₃ is the azido group (--N₃).
 5. A compound according toclaim 4, whereineach of R₇ and R₈ is methyl.
 6. A compound according toclaim 4, selected from the group of the following azidocompounds:N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2-methyl-6-azido-aniline,N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-azido-aniline,N-(1'-methoxycarbonyl-ethyl)-N-(2-tetrahydrofuryl-carbonyl)-2-methyl-6-azido-aniline,N-(1'-methoxycarbonyl-3'-hydroxy-n-propyl)-N-methoxyacetyl-2-methyl-6-azido-aniline,N-(1'-methoxycarbonyl-ethyl)-N-methylaminosulfonyloxyacetyl-2,6-dimethyl-3-azido-aniline,N-(1'-methoxycarbonyl-3-hydroxy-n-propyl)-N-cyclopropylcarbonyl-2-methyl-6-azido-aniline,andN-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2,3-dimethyl-6-azido-aniline.7. N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2-methyl-6-azido-anilineaccording to claim
 6. 8. A composition for combating and/or preventingan infestation by harmful microorganisms, which composition contains asactive ingredient at least one active substance according to claim 1 andan inert carrier.
 9. A composition according to claim 8, which contains0.1 to 99 percent by weight of the active substance 1 to 99 percent byweight of additives, and 0 to 25 percent by weight of a surface-activeagent.
 10. A composition according to claim 9, which contains 0.1 to 95percent by weight of the active substance.
 11. A composition accordingto claim 10, which contains 0.1 to 25 percent by weight of asurface-active agent.
 12. A process for combating and/or preventing aninfestation of plants by phytopathogenic microorganisms, which processcomprises applying an effective amount of a compound according to anyone of claims 1 to 6, in diluted form, to the plants or to the locusthereof.
 13. A process for combating and/or preventing an infestation ofplants by phytopathogenic fungi, which process comprises applying afungicidally effective amount of a compound according to any one ofclaims 1 to 6, in diluted form, to the plants or to the locus thereof.